在本論文中，我們主要探討雙偶極性主體材料於有機發光二極體之應用。首先，在第二章中我們設計並合成了五個含蒽之菲並咪唑主體材料，藉由引入五種不同推電子能力的官能基，使材料具有雙偶極性的效果，有利於元件中載子傳遞的平衡。而我們在菲並咪唑、蒽基以及推電子官能基之間引入兩個苯環結構，則可斷開共軛，確保主體材料高能隙的特性(Eg >3.0 eV)。此一系列主體材料的熱裂解溫度皆高於450 ℃，玻璃轉化溫度也都高於140 ℃，具有十分優良的熱穩定性。將客體材料BCzVBi摻雜入此系列主體材料後，以PIAAn為主體材料的元件具有最佳的效率表現，其最大外部量子效率、發光效率與發光功率分別為10.1%、12.9 cd/A與10.9 lm/W，CIEx,y色度座標位於(0.15, 0.14)，屬於深藍光的放光。而元件的高效率除了來自PIAAn優良的載子平衡能力外，此系列主體材料也使客體材料(BCzVBi)的偶極矩於發光層中趨向水平排列(Θ = 0.89~0.92)，大幅提升元件的出光率。此外，我們將表現最佳的主體材料PIAAn應用於橘色以及白色螢光元件中，皆具有不錯的元件表現，其中以Rubrene為客體材料的橘色螢光元件最大外部量子效率、發光效率與發光功率分別為6.9%、25.7 cd/A與26.8 lm/W，CIEx,y色度座標位於(0.48, 0.52)。而綜合PIAAn、BCzVBi與Rubrene所製成的單一發光層的白色螢光元件，其最大外部量子效率、發光效率與發光功率則分別為7.5%、9.3 cd/A與8.3 lm/W，CIEx,y色度座標位於(0.27, 0.34)，此系列白光元件具有十分穩定的光色表現且元件效率的滾降(Roll-off)現象十分輕微。
在第三章中，我們則探討TADF型激發複合體(Exciplex)的作用機制，其中我們以具有雙偶極性的紫光材料BT-03作為電子予體(主體材料)，搭配TADF型水藍光材料2CzPN為電子受體(客體材料)，製作出一系列具TADF特性的高效率綠光激發複合體元件，其最大外部量子效率、發光效率與發光功率則分別為18.0%、57.8 cd/A與51.6 lm/W，CIEx,y色度座標位於(0.32, 0.51)。此外，我們也將BT-03搭配4CzIPN與CzDBA兩TADF型綠光材料作為電子受體(客體材料)，製作出兩組具TADF特性的橘光激發複合體元件，其中以CzDBA為客體材料之元件具有十分出色的效率表現，其最大外部量子效率、發光效率與發光功率則分別為19.2%、54.7 cd/A與48.9 lm/W，CIEx,y色度座標位於(0.50, 0.48)。最後，我們也藉由上述三組激發複合體之螢光量子效率與延遲螢光生命期之量測，進一步解釋並預測電子予體與電子受體之化學結構對激發複合體元件效率表現的影響。

In this thesis, we mainly focus on the applications of bipolar host materials in organic light-emitting diodes. In Chapter 2, five bipolar host materials based on electron-deficient phenanthroimidazole and anthracene derivatives, PIAAn, PIACzph, PIACz, PIAPhCz and PIADPA have been designed and synthesized, in which the incorporation of five different donor units facilitates the charge balance in the devices. On the other hand, the phenyl units are introduced to reduce the degree of π-conjugation between donor and acceptor units, resulting in a high singlet energy for these host materials. These compounds exhibit excellent thermal stability with decomposition temperature above 450 ℃ and glass transition temperature above 140 ℃. Moreover, the device using PIAAn doped with 5 wt% BCzVBi as emitting layer shows a maximum external quantum efficiency (E.Q.E.) of 10.1%, the current efficiency (C.E.) of 12.9 cd/A, and the power efficiency (P.E.) of 10.9 lm/W with the CIE coordinates of (0.15, 0.14). The outstanding performances of the device can be attributed to highly preferred horizontal transition dipole ratio (Θ) of 0.89~0.92 as well as its perfect charge balance ability. Furthermore, we apply the host material, PIAAn, into the orange and white fluorescent OLEDs and the orange device using Rubrene as guest material displays a maximum E.Q.E. of 6.9%, the C.E. of 25.7 cd/A, and the P.E. of 26.8 lm/W with the CIE coordinates of (0.48, 0.52). The white device with the single emitting layer composed of PIAAn, BCzVBi, and Rubrene gives a maximum E.Q.E. of 7.5%, the C.E. of 9.3 cd/A, and the P.E. of 8.3 lm/W with the CIE coordinates of (0.27, 0.34), featuring stable EL performances and low efficiency roll-off as well.
In Chapter 3, we attempt to discuss the mechanism of the TADF-type exciplex system. First of all, we fabricate a series of devices utilizing bipolar host material, BT-03, as electron donor, doped with TADF-type guest material, 2CzPN, as electron acceptor. The resulting green fluorescent device which demonstrates a TADF characteristic exhibits a high E.Q.E. of 18.0%, the C.E. of 57.8 cd/A, and the P.E. of 51.6 lm/W with the CIE coordinates of (0.32, 0.51). On the other hand, we fix BT-03 as electron donor and choose another two TADF-type materials, 4CzIPN and CzDBA, as electron acceptor, and successfully fabricate two series of orange fluorescent devices with TADF characteristics. The one using CzDBA as electron acceptor achieves a high E.Q.E. of 19.2%, the C.E. of 54.7 cd/A, and the P.E. of 48.9 lm/W with the CIE coordinates of (0.50, 0.48). Finally, we further explain and predict the relationships between the structure of electron donor and electron acceptor in the emitting layer and the device performances of exciplex system via the measurement of quantum efficiency and delay fluorescence lifetime of the three exciplex systems discussed above.

第一章
(1) Kim, S. T. In the 6th International Meeting on Information Display and the International Display Manufacturing Conference (IMID/IDMC 2006) Daegu, Korea, 2006.
(2) Destriau, G. J. Chem. Phys. 1936, 33, 587.
(3) Pope, M.; Kallmann, H. P.; Magnante, P. J. Chem. Phys. 1963, 38, 2042.
(4) Tang, C. W.; VanSlyke, S. A. Appl. Phys. Lett. 1987, 51, 913.
(5) Tang, C. W.; VanSlyke, S. A.; Chen, C. H. J. Appl. Phys. 1989, 65, 3610.
(6) Forster, T. Disc. Faraday Soc. 1959, 27, 7.
(7) Dexter, D. L. J. Chem. Phys. 1953, 21, 836.
(8) Adachi, C. N., H. Matrerial Matters 2009, 4.3, 74.
(9) 何孟寰，黃孝文，陳金鑫 有機電激磷光材料與OLED磷光元件之發展近況, 2005; Vol. 63.
(10) Liu, S. W.; Wang, J. X.; Divayana, Y.; Dev, K.; Tan, S. T.; Demir, H. V.; Sun, X. W. Appl. Phys. Lett. 2013, 102, 053305.
(11) Azenha, E. l. G.; Serra, A. C.; Pineiro, M.; Pereira, M. M.; Seixas de Melo, J.; Arnaut, L. G.; Formosinho, S. J.; Rocha Gonsalves, A. M. d. A. Chem. Phys. 2002, 280, 177.
(12) Baldo, M. A.; O’Brien, D. F.; Thompson, M. E.; Forrest, S. R. Phys. Rev. B 1999, 60, 14422.
(13) Tao, Y.; Yuan, K.; Chen, T.; Xu, P.; Li, H.; Chen, R.; Zheng, C.; Zhang, L.; Huang, W. Adv. Mater. 2014, 26, 7931.
(14) Méhes, G.; Nomura, H.; Zhang, Q.; Nakagawa, T.; Adachi, C. Angew .Chem. Int. Ed. 2012, 51, 11311.
(15) Lee, J.; Shizu, K.; Tanaka, H.; Nomura, H.; Yasuda, T.; Adachi, C. J. Mater. Chem. C 2013, 1, 4599.
(16) Tsang, D. P.-K.; Matsushima, T.; Adachi, C. Sci. Rep. 2016, 6, 22463.
(17) Chou, P. Y.; Chou, H. H.; Chen, Y. H.; Su, T. H.; Liao, C. Y.; Lin, H. W.; Lin, W. C.; Yen, H. Y.; Chen, I. C.; Cheng, C. H. Chem. Commun. 2014, 50, 6869.
(18) Di, D.; Yang, L.; Richter, J. M.; Meraldi, L.; Altamimi, R. M.; Alyamani, A. Y.; Credgington, D.; Musselman, K. P.; MacManus-Driscoll, J. L.; Friend, R. H. Adv. Mater. 2017, 29, 1605987.
(19) In COMSOL Conference Boston, 2015.
(20) 陳金鑫，黃孝文 OLED夢幻顯示器．OLED材料與元件, 2009.
(21) Bulović, V.; Khalfin, V. B.; Gu, G.; Burrows, P. E.; Garbuzov, D. Z.; Forrest, S. R. Phys. Rev. B 1998, 58, 3730.
(22) Lin, H.-W.; Lin, C.-L.; Chang, H.-H.; Lin, Y.-T.; Wu, C.-C.; Chen, Y.-M.; Chen, R.-T.; Chien, Y.-Y.; Wong, K.-T. J. Appl. Phys. 2004, 95, 881.
(23) Yokoyama, D.; Sakaguchi, A.; Suzuki, M.; Adachi, C. Appl. Phys. Lett. 2008, 93, 173302.
(24) Yokoyama, D.; Sakaguchi, A.; Suzuki, M.; Adachi, C. Appl. Phys. Lett. 2009, 95, 243303.
(25) Yokoyama, D. J. Mater. Chem. 2011, 21, 19187.
(26) Frischeisen, J.; Yokoyama, D.; Endo, A.; Adachi, C.; Brütting, W. Org. Electron. 2011, 12, 809.
(27) Yokoyama, D.; Sasabe, H.; Furukawa, Y.; Adachi, C.; Kido, J. Adv. Funct. Mater. 2011, 21, 1375.
(28) Kim, K.-H.; Lee, S.; Moon, C.-K.; Kim, S.-Y.; Park, Y.-S.; Lee, J.-H.; Woo Lee, J.; Huh, J.; You, Y.; Kim, J.-J. Nat. Commun. 2014, 5, 4769.
第二章
(1) Kim, K.-H.; Lee, S.; Moon, C.-K.; Kim, S.-Y.; Park, Y.-S.; Lee, J.-H.; Woo Lee, J.; Huh, J.; You, Y.; Kim, J.-J. Nat. Commun. 2014, 5, 4769.
(2) Lee, M.-T.; Chen, H.-H.; Liao, C.-H.; Tsai, C.-H.; Chen, C. H. Appl. Phys. Lett. 2004, 85, 3301.
(3) Lee, M. T.; Liao, C. H.; Tsai, C. H.; Chen, C. H. Adv. Mater. 2005, 17, 2493.
(4) Kim, M.-S.; Choi, B.-K.; Lee, T.-W.; Shin, D.; Kang, S. K.; Kim, J. M.; Tamura, S.; Noh, T. Appl. Phys. Lett. 2007, 91, 251111.
(5) Lyu, Y.-Y.; Kwak, J.; Kwon, O.; Lee, S.-H.; Kim, D.; Lee, C.; Char, K. Adv. Mater. 2008, 20, 2720.
(6) Kuo, C.-J.; Li, T.-Y.; Lien, C.-C.; Liu, C.-H.; Wu, F.-I.; Huang, M.-J. J. Mater. Chem. 2009, 19, 1865.
(7) Liu, D.; Du, M.; Chen, D.; Ye, K.; Zhang, Z.; Liu, Y.; Wang, Y. J. Mater. Chem. C 2015, 3, 4394.
(8) 周鶴修 博士論文, 2010.
(9) 許郃珮 碩士論文, 2011.
(10) Islangulov, R. R.; Castellano, F. N. Angew .Chem. Int. Ed. 2006, 45, 5957.
(11) Gray, V.; Dzebo, D.; Lundin, A.; Alborzpour, J.; Abrahamsson, M.; Albinsson, B.; Moth-Poulsen, K. J. Mater. Chem. C 2015, 3, 11111.
(12) Di, D.; Yang, L.; Richter, J. M.; Meraldi, L.; Altamimi, R. M.; Alyamani, A. Y.; Credgington, D.; Musselman, K. P.; MacManus-Driscoll, J. L.; Friend, R. H. Adv. Mater. 2017, 29, 1605987.
(13) Jones, R. N. Chem. Rev. 1947, 41, 353.
(14) You, D. K.; Lee, S. H.; Lee, J. H.; Kwak, S. W.; Hwang, H.; Lee, J.; Chung, Y.; Park, M. H.; Lee, K. M. RSC Adv. 2017, 7, 10345.
(15) Wong, K.-T.; Ku, S.-Y.; Cheng, Y.-M.; Lin, X.-Y.; Hung, Y.-Y.; Pu, S.-C.; Chou, P.-T.; Lee, G.-H.; Peng, S.-M. J. Org. Chem. 2006, 71, 456.
(16) Chou, P.-T.; Yu, W.-S.; Cheng, Y.-M.; Pu, S.-C.; Yu, Y.-C.; Lin, Y.-C.; Huang; Chen, C.-T. J. Phys. Chem. A 2004, 108, 6487.
(17) Naito, K. Chem. Mater. 1994, 6, 2343.
(18) Salbeck, J.; Yu, N.; Bauer, J.; Weissörtel, F.; Bestgen, H. Synth. Met. 1997, 91, 209.
(19) J. Shi, C. W. T., C. H. Chen U.S. Patent 5646948, 1997.
(20) Tian, G.; Huang, W.; Cai, S.; Zhou, H.; Li, B.; Wang, Q.; Su, J. RSC Adv. 2014, 4, 38939.
(21) Hosokawa, C.; Higashi, H.; Nakamura, H.; Kusumoto, T. Appl. Phys. Lett. 1995, 67, 3853.
(22) Malliaras, G. G.; Scott, J. C. J. Appl. Phys. 1998, 83, 5399.
(23) 梁從主，陳琬鎔，曾偉菁 In 科學發展月刊 2013; Vol. 491, p 58.
(24) Chen, Y.-H.; Lin, C.-C.; Huang, M.-J.; Hung, K.; Wu, Y.-C.; Lin, W.-C.; Chen-Cheng, R.-W.; Lin, H.-W.; Cheng, C.-H. Chem. Sci. 2016, 7, 4044.
(25) Williams, D. F. J. Chem. Phys. 1967, 47, 344.
(26) Seo, J. H.; Park, J. S.; Seo, B. M.; Han, W. K.; Lee, K. H.; Park, J. K.; Yoon, S. S.; Kim, Y. K. Mol. Cryst. Liq. Cryst. 2011, 538, 84.
(27) Chen, Y.-H.; Chou, H.-H.; Su, T.-H.; Chou, P.-Y.; Wu, F.-I.; Cheng, C.-H. Chem. Commun. 2011, 47, 8865.
(28) Seo, J. H.; Lee, S. J.; Hyung, G. W.; Lee, K. H.; Park, J. K.; Yoon, S. S.; Kim, Y. K. J. Nanosci. Nanotechnol. 2011, 11, 5812.
(29) Park, H.; Lee, J.; Kang, I.; Chu, H. Y.; Lee, J.-I.; Kwon, S.-K.; Kim, Y.-H. J. Mater. Chem. 2012, 22, 2695.
(30) Li, Z.; Jiao, B.; Wu, Z.; Liu, P.; Ma, L.; Lei, X.; Wang, D.; Zhou, G.; Hu, H.; Hou, X. J. Mater. Chem. C 2013, 1, 2183.
(31) Meng, M.; Song, W.; Kim, Y.-H.; Lee, S.-Y.; Jhun, C.-G.; Zhu, F. R.; Ryu, D. H.; Kim, W.-Y. J. Nanosci. Nanotechnol. 2013, 13, 294.
(32) Li, C.; Zhang, M.; Chen, X.; Li, Q. Opt. Mater. Express 2016, 6, 2545.
(33) 孫于雯 碩士論文, 2016.
(34) Liduo, W.; Lian, D.; Gangtie, L.; Yong, Q. Jpn. J. Appl. Phys. 2004, 43, L560.
(35) Wu, Y.-S.; Liu, T.-H.; Chen, H.-H.; Chen, C. H. Thin Solid Films 2006, 496, 626.
(36) Singh-Rachford, T. N.; Castellano, F. N. J. Phys. Chem. A 2008, 112, 3550.
(37) Chen, S.; Wu, Q.; Kong, M.; Zhao, X.; Yu, Z.; Jia, P.; Huang, W. J. Mater. Chem. C 2013, 1, 3508.
第三章
(1) Tao, Y.; Yuan, K.; Chen, T.; Xu, P.; Li, H.; Chen, R.; Zheng, C.; Zhang, L.; Huang, W. Adv. Mater. 2014, 26, 7931.
(2) Wong, M. Y.; La-Placa, M.-G.; Pertegas, A.; Bolink, H. J.; Zysman-Colman, E. J. Mater. Chem. C 2017, 5, 1699.
(3) Uoyama, H.; Goushi, K.; Shizu, K.; Nomura, H.; Adachi, C. Nature 2012, 492, 234.
(4) Yang, Z.; Mao, Z.; Xie, Z.; Zhang, Y.; Liu, S.; Zhao, J.; Xu, J.; Chi, Z.; Aldred, M. P. Chem. Soc. Rev. 2017, 46, 915.
(5) Im, J. B.; Lampande, R.; Kim, G. H.; Lee, J. Y.; Kwon, J. H. J. Phys. Chem. C 2017, 121, 1305.
(6) Chen, D.; Wang, Z.; Wang, D.; Wu, Y.-C.; Lo, C.-C.; Lien, A.; Cao, Y.; Su, S.-J. Org. Electron. 2015, 25, 79.
(7) Goushi, K.; Yoshida, K.; Sato, K.; Adachi, C. Nat. Photonics 2012, 6, 253.
(8) Goushi, K.; Adachi, C. Appl. Phys. Lett. 2012, 101, 023306.
(9) Li, J.; Nomura, H.; Miyazaki, H.; Adachi, C. Chem. Commun. 2014, 50, 6174.
(10) Liu, X.-K.; Chen, Z.; Zheng, C.-J.; Liu, C.-L.; Lee, C.-S.; Li, F.; Ou, X.-M.; Zhang, X.-H. Adv. Mater. 2015, 27, 2378.
(11) Liu, W.; Chen, J.-X.; Zheng, C.-J.; Wang, K.; Chen, D.-Y.; Li, F.; Dong, Y.-P.; Lee, C.-S.; Ou, X.-M.; Zhang, X.-H. Adv. Funct. Mater. 2016, 26, 2002.
(12) Hung, W.-Y.; Wang, T.-C.; Chiang, P.-Y.; Peng, B.-J.; Wong, K.-T. ACS Appl. Mater. Interfaces 2017, 9, 7355.
(13) Lee, D. R.; Hwang, S.-H.; Jeon, S. K.; Lee, C. W.; Lee, J. Y. Chem. Commun. 2015, 51, 8105.
(14) Zhang, Q.; Li, B.; Huang, S.; Nomura, H.; Tanaka, H.; Adachi, C. Nat. Photonics 2014, 8, 326.
(15) Lin, C.-C.; Huang, M.-J.; Chiu, M.-J.; Huang, M.-P.; Chang, C.-C.; Liao, C.-Y.; Chiang, K.-M.; Shiau, Y.-J.; Chou, T.-Y.; Chu, L.-K.; Lin, H.-W.; Cheng, C.-H. Chem. Mater. 2017, 29, 1527.
(16) Tian, G.; Huang, W.; Cai, S.; Zhou, H.; Li, B.; Wang, Q.; Su, J. RSC Adv. 2014, 4, 38939.
(17) Wang, S.; Wang, X.; Yao, B.; Zhang, B.; Ding, J.; Xie, Z.; Wang, L. Sci. Rep. 2015, 5, 12487.
(18) Masui, K.; Nakanotani, H.; Adachi, C. Org. Electron. 2013, 14, 2721.
(19) Chen, D.; Xie, G.; Cai, X.; Liu, M.; Cao, Y.; Su, S.-J. Adv. Mater. 2016, 28, 239.
(20) Hung, W.-Y.; Fang, G.-C.; Lin, S.-W.; Cheng, S.-H.; Wong, K.-T.; Kuo, T.-Y.; Chou, P.-T. Sci. Rep. 2014, 4, 5161.
(21) Hung, W.-Y.; Fang, G.-C.; Chang, Y.-C.; Kuo, T.-Y.; Chou, P.-T.; Lin, S.-W.; Wong, K.-T. ACS Appl. Mater. Interfaces 2013, 5, 6826.
(22) Sang Kyu, J.; Kyoung Soo, Y.; Jun Yeob, L. Nanotechnology 2016, 27, 224001.